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I realized today how much I love instrumental opening songs. I usually feel that an instrumental opening establishes the feel for an anime much better than songs with vocals - this isn't always the case, of course, but all the series that I can think of with instrumental openings always had the opening going for them.

These are the series which I know and love that have instrumental openings:

GunGrave
Gad Guard
Monster
Texhnolyze

I'm sure there are lots of series that have instrumental openings that I don't know of. I would love to hear everyone else's opinions and suggestions on this.

the first and third Tenchi Muyo! OVAs have instrumental openings, and the original El-Hazard OVA was done with an all-classical style soundtrack (except the ending). 12 Kingdoms also has a very grandiose symphonic theme song.

ShingetsutanTsukihime and Read or Die OVA/TV have instrumental openings as well. Tsukihime has a dark-themed classical piece for its opening while Read or Die uses a more jazzy piece. Cowboy Bebop also has a jazzy opening.

And just as others have mentioned, other instrumental greats are found in the original El Hazard OVA, Haibane Renmei and Twelve Kingdoms (Juuni Kokki). If memory serves me correctly, I think Ninja Scroll TV has an instrumental opening as well. (This one didn't particularly appeal to me though.)

The Tsukihime opening is called 'Sacred Moon'. Though, I'm not sure if it's really a pure instrumental. There are some sounds of what seems like chanting, but that could just be me... I can't make out the words, if they're there.